US3882133A - Manufacture of bipyridyls - Google Patents
Manufacture of bipyridyls Download PDFInfo
- Publication number
- US3882133A US3882133A US303957A US30395772A US3882133A US 3882133 A US3882133 A US 3882133A US 303957 A US303957 A US 303957A US 30395772 A US30395772 A US 30395772A US 3882133 A US3882133 A US 3882133A
- Authority
- US
- United States
- Prior art keywords
- pyridine
- salt
- quaternised
- parts
- bipyridyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- -1 alkyl pyridines Chemical class 0.000 claims abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 101
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 20
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 17
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical group [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012346 acetyl chloride Substances 0.000 claims description 4
- KGKAYWMGPDWLQZ-UHFFFAOYSA-N 1,2-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1CBr KGKAYWMGPDWLQZ-UHFFFAOYSA-N 0.000 claims description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000004821 distillation Methods 0.000 description 2
- KUGJZWMREKOLDN-UHFFFAOYSA-N 1,2-dibromoethane pyridine Chemical compound BrCCBr.C1=CC=NC=C1 KUGJZWMREKOLDN-UHFFFAOYSA-N 0.000 description 1
- HLNJFEXZDGURGZ-UHFFFAOYSA-M 1-methylpyridin-1-ium;iodide Chemical compound [I-].C[N+]1=CC=CC=C1 HLNJFEXZDGURGZ-UHFFFAOYSA-M 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
Definitions
- a process for the manufacture of 2,2'-bipyridyl and alkyl derivatives thereof which comprises heating pyridine or an alkyl derivative thereof having at least one free a-position with a salt of a pyridine or of a quaternised pyridine in which the quaternising group is an aliphatic or cycloaliphatic group or substituted derivative thereof.
- alkyl derivatives of pyridine there are mentioned especially a, B and 'y-picoline, but pyridines containing higher alkyl groups or more than one alkyl group may be used as long as there is a free a-position.
- the salt may be derived from pyridine itself or for example from alkyl pyridines, especially from alkylpyridines having a free oz-position, or from 2,2-dipyridyl itself, or from radicals derived from these by quaternisation.
- alkyl pyridines especially from alkylpyridines having a free oz-position, or from 2,2-dipyridyl itself, or from radicals derived from these by quaternisation.
- halides particularly chlorides and bromides.
- pyridine hydrochloride which may be preformed or prepared in situ by adding hydrogen chloride to the pyridine.
- the salt of a quaternised pyridine may be preformed by well-known and conventional methods for use in the process or may be prepared in situ from an appropriate pyridine and quaternising agent.
- quaternising agents which may be used to prepare quaternary salts for use in the process there are mentioned methyl iodide, ethylene dichloride, ethylene dibromide, acetyl chloride, a, a'-dichloroacetone, and oxylylenedibromide.
- the salt be derived from the same pyridine (whether quaternised or not), especially pyridine itself, that is used in the process of the invention.
- the process of the invention may be carried out by mixing the pyridine or alkyl derivative thereof with either the salt or with an appropriate acid or quatemising agent and heating the mixture in a sealed vessel to a temperature between 300 and 400C.
- the preferred reaction temperatures are between 320 and 350C.
- the reaction time will depend upon the reaction temperature but it is usually preferred to use at least 3 hours.
- Any amount of salt or ingredients thereof down to about 2% of the weight of pyridine may conveniently be used, but it is preferred to use between 4 and 40% of the weight of pyridine.
- the 2,2-bipyridyl may be isolated from the reaction mixture in any conventional manner, for example by removal of the pyridine by distillation at atmospheric pressure, and distillation of the 2,2-bipyridyl at reduced pressure.
- EXAMPLE 2 Ethylene dichloride (3 parts) and pyridine (25 parts) were heated at 340C for 10 hours. Analysis showed the formation of 2.15 parts of 2,2'-bipyridyl.
- a process for the manufacture of 2,2-bipyridyl and dimethyl derivatives thereof which comprises heating at a temperature of between 300 and 400C.
- pyridine or a, ,6 or 'y-picoline with from 2 to 40% of its weight of a halide salt of pyridine or of a quaternised pyridine the pyridine being selected from pyridine itself, a, B or 'y-picoline and 2,2'-dipyridyl and the quaternised group being derived from a member selected from the group consisting of methyl iodide, ethylene dichloride, ethylene dibromide, acetyl chloride, at, a'-dichloroacetone or o-xylylene dibromide and wherein from 2% to 40% of the salt, based on the weight of the pyridine, is used.
- a process as claimed in claim 1 wherein the salt of a pyridine is pyridine hydrochloride.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5293671A GB1399099A (en) | 1971-11-15 | 1971-11-15 | Manufacture of bipyridyls |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3882133A true US3882133A (en) | 1975-05-06 |
Family
ID=10465896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US303957A Expired - Lifetime US3882133A (en) | 1971-11-15 | 1972-11-06 | Manufacture of bipyridyls |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3882133A (instruction) |
| JP (1) | JPS4861480A (instruction) |
| AU (1) | AU477017B2 (instruction) |
| CS (1) | CS176211B2 (instruction) |
| DD (1) | DD100946A5 (instruction) |
| DE (1) | DE2255205A1 (instruction) |
| FR (1) | FR2160456B1 (instruction) |
| GB (1) | GB1399099A (instruction) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3962268A (en) * | 1974-05-22 | 1976-06-08 | Imperial Chemical Industries Limited | Process for producing 2:2'- or 4:4'-bipyridyls |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4158093A (en) * | 1977-12-15 | 1979-06-12 | Reilly Tar & Chemical Corporation | Process for substituting and dequaternizing pyridylethyl quaternary salts of pyridine and bypyridine bases |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3697534A (en) * | 1968-10-03 | 1972-10-10 | Ici Ltd | Preparation of 2,2{40 -bipyridyl |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1338399A (en) * | 1970-08-17 | 1973-11-21 | Ici Ltd | Manufacture of bipyridyls |
-
1971
- 1971-11-15 GB GB5293671A patent/GB1399099A/en not_active Expired
-
1972
- 1972-11-06 US US303957A patent/US3882133A/en not_active Expired - Lifetime
- 1972-11-09 AU AU48665/72A patent/AU477017B2/en not_active Expired
- 1972-11-10 DE DE2255205A patent/DE2255205A1/de active Pending
- 1972-11-10 CS CS7629A patent/CS176211B2/cs unknown
- 1972-11-14 FR FR7240373A patent/FR2160456B1/fr not_active Expired
- 1972-11-15 DD DD167182A patent/DD100946A5/xx unknown
- 1972-11-15 JP JP47114623A patent/JPS4861480A/ja active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3697534A (en) * | 1968-10-03 | 1972-10-10 | Ici Ltd | Preparation of 2,2{40 -bipyridyl |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3962268A (en) * | 1974-05-22 | 1976-06-08 | Imperial Chemical Industries Limited | Process for producing 2:2'- or 4:4'-bipyridyls |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2255205A1 (de) | 1973-05-24 |
| AU477017B2 (en) | 1976-10-14 |
| GB1399099A (en) | 1975-06-25 |
| FR2160456B1 (instruction) | 1976-08-20 |
| FR2160456A1 (instruction) | 1973-06-29 |
| CS176211B2 (instruction) | 1977-06-30 |
| DD100946A5 (instruction) | 1973-10-12 |
| AU4866572A (en) | 1974-05-09 |
| JPS4861480A (instruction) | 1973-08-28 |
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